Lubricating oil composition



United States Patent Office LUBRIQATHVG OIL COB/ POSITION Robert E.Karll, Hammond, Albert R. Sabol, Munster, and Eugene E. Richardson,Hammond, 11141., assiguors to Standard Oil Company, Chicago, 111., acorporation of Indiana No Drawing. Application July 29, 1955 Serial No.525,386

6 Claims. (Cl. 25.2-32.7)

This invention relates to a novel lubricating oil composition and moreparticularly pertains to a lubricating oil composition having improveddetergency characteristics.

In the lubrication of internal combustion engines of all types,particularly when severe operating conditions are encountered, plainlubricating oils often prove unsatisfactory because of the oxidativedeterioration of the oil with the attendant deposition on the enginesurfaces of varnish, gum and sludge and the formation of acidiccompounds resulting in corrosion of the metal surfaces of the engine.

It has heretofore been discovered that certain reaction products of aphosphorus sulfide and a hydrocarbon, particularly an olefin or anolefin polymer, when added in small amounts to a hydrocarbon oil, areeffective in inhibiting the formation of varnish, sludge, carbon and thelike in lubricating oils during use. It has also been found thatneutralizing these reaction products of a phosphorus sulfide and ahydrocarbon with a basic reagent having a metal constituent andparticularly with a basic barium compound provides a composition whichis effective as a detergent. However, it has since been found that undercertain conditions, particularly when high sulfur fuels are employed,lubricants containing the neutralized, metal contaim'ng product of aphosphorus sulfide and a hydrocmbon does not effectively inhibit theformation of sludge, varnish and other resinous materials in the engineor provide adequate detergency.

it is an object of the present invention to provide a lubricant forinternal combustion engines which will be effective in providingadequate lubrication for such engines. It is a further object of theinvention to provide a lubricant additive which serves the functions of(1) inhibiting the oxidative deterioration of the lubricant, (2)preventing corrosion of the lubricated surfaces, and (3) acting as adetergent to prevent ring sticking, varnishing or coating of themetallic surfaces of internal combustion engines, as well as asuspending or dispersing agent for dispersing very small particles ofdeterioration products or contaminating materials in the oil. A moreparticular object is to provide a lubricant additive to serve the aboveenumerated functions when employed in an internal combustion engineusing a fuel containing a relatively high percentage of sulfur. Theseand additional objects will become apparent as the description of theinvention proceeds.

We have discovered that a product havin the desired carbon and/orvarnish formation inhibiting properties as well as improved corrosioninhibiting properties and detergent properties can be obtained byincorporating in a lubricant composition, provided with a metalcontaining neutralized reaction product of a phosphorus sulfide and ahydrocarbon, and particularly a barium containing neutralized reactionproduct of a phosphorus sulfide and an olefin, a small amount of acompound prepared by reacting a basic metal compound,

preferably a basic alkali metal or alkaline earth metal compound, and analkyl alcohol having from 5 to 30 carbon atoms, and preferably from 8 to20 carbon atoms, or an alkyl phenol having from 8 to 36 carbon atoms,and preferably from 12 to 26 carbon atoms; and contacting said reactionproduct with carbon dioxide. Reaction of the basic metal compound andthe hydroxy compound may be carried out at a temperature from about 0 F.to about 400 F. and preferably in the range of from about F. to about350 F. The reaction of carbon dioxide and the intermediate reactionproduct may be carried out at a temperature in the range of from about 0F. to about 300 F. and preferably in the range of from about F. to about250 F.

It has been found that from 0.01% to about 10% and preferably from about0.10% to about 2% of this addition agent in a lubricating oil containingfrom about 0.001% to 10% of a metal containing neutralized reactionproduct of a phosphorus sulfide and a hydrocarbon provides a lubricatingoil having excellent detergent characteristics Which is effectivelyinhibited against the formation of varnish, sludge, carbon or the like.

While the hereinbefore described reaction product of a basic metalcompound, a hydroxy compound and carbon dioxide can be used incombination with the here inafter described phosphorussulfide-hydrocarbon reaction product, it is often desirable to employthe former product in combination with the phosphorussulfide-hydrocarbon reaction product and an organic sulfur compound asdescribed and claimed in US. Re. 22,464, issued to Kelso et al. April 4,1944, or a sulfurized terpene as described and claimed in US. 2,422,585issued to T. H. Rogers et al. June 17, 1947.

While the reaction product of a basic metal compound, a hydroxy compoundand carbon dioxide in the hereinbefore described class are effective inincreasing the detergency of a lubricating oil in the presence of themetal containing neutralized reaction product of a phosphorus sulfideand a hydrocarbon, it is not to be implied that all are equallyeffective since the effectiveness can vary with the type of lubricatingoil and the conditions of use.

As aforesaid, one of the components of the improved lubricant is theneutralized reaction product of a hydrocarbon and a phosphorus sulfidesuch as P 8 P 8 P 8 or other phosphorus sulfides, and preferablyphosphorus pentasulfide, P 8 The hydrocarbon constituent of thisreaction is preferably a mono-olefin hydrocarbon polymer resulting fromthe polymerization of low molecular weight mono-olefinic hydrocarbons orisomonoolefin hydrocarbons such as propylenes, butylenes, and amylenesor the copolymers obtained by the polymerization of hydrocarbon mixturescontaining isomono-olefins and mono-olefins of less than 6 carbon atoms.The polymers may be obtained by the polymerization of these olefins ormixtures of olefins in the presence of a catalyst such as sulfuric acid,phosphoric acid, boron fluoride, aluminum chloride or other similarhalide catalysts of the Friedel-Crafts type.

The polymers employed are preferably mono-olefin polymers or mixtures ofmono-olefin polymers and isomono-olefin polymers having molecularweights ranging from about to about 50,000 or more, and preferably fromabout 500 to about 10,000. Such polymers can be obtained, for example,by the polymerization in the liquid phase of a hydrocarbon mixturecontaining mono-olefins and isomono-olefins such as butylene andisobutylene at a temperature of from about -80 F. to

about 100 F. in the presence of a metal halide catalystof theFriedel-Crafts type such as, for example, boron Patented Jan. 19, 1960aration of these polymers we may employ, for example, a hydrocarbonmixture containing isobutylene, butylenes and butanes recovered frompetroleum gases, especially those gases produced in the cracking ofpe.roleurn oils in the manufacture of gasoline.

- A suitable polymer for the reaction with phosphorus sulfide is theproduct obtained by polymerizing in the liquid phase a hydrocarbonmixture containing butylenes and isobutylenes together with butanesandsome C and C hydrocarbons at a temperature between about 0 F. and 30F. in the presence of aluminum chloride. A suitable method for carryingout the polymerization is to introduce the aluminum chloride into thereactor and introduce the hydrocarbon mixture cooled to a temperature ofabout 0 F. into the bottom of the reactor and pass it upwardly throughthe catalyst layer while regulating the temperature within the reactorso that the polymer product leaving the top of the reactor is at atemperature of about 30 F. After separating the polymer from thecatalyst sludge and unreacted hydrocarbon, the

. polymer is fractionated to obtain a fraction of the desired viscositysuch as, for example, from about 80 seconds to about 2000 secondsSaybolt Universal at 210 F.

' Another suitable polymer is that obtained by polymerizing in theliquidphase a hydrocarbon mixture comprising substantially Chydrocarbons in the presence of an aluminum chloride-complex catalyst.The catalyst is preferably prepared by heating aluminum chloride withiso-octane. The hydrocarbon mixture is introduced into the bottom of thereactor and passed upwardly through the catalyst layer, while atemperature of from about 50 F. to about 110 F. is maintained in thereactor. The propane and other saturated gases pass through thecatalyst, while the propylene is polymerized under these conditions. Thepropylene polymer can be fractionated to any desired molecular weight,preferably from about 500 to about 1000 or higher. Y Other suitablepolymers can be obtained by polymerizing a hydrocarbon mixturecontaining about to about 25% isobutylene at a temperature of from about0 Fpto about 100 F. and preferably 0 F. to about 32 F. in the presenceof boron fluoride. After'the polymerization of the isobutylene togetherwith a relatively minor amount of the normal olefins present,'thereaction mass is neutralized, washed free of acidic substances and theunreacted hydrocarbons subsequently separated from the polymers bydistillation. The polymer mixture so obtained, depending upon thetemperature of reaction, varies in consistency from a light liquid toviscous, oily material and contains polymers having molecular weightsranging from about 100 to about 2000 or higher. The polymers so obtainedmay be used as such, or the polymer may be fractionated under reducedpressure into fractions of increasing molecular weights, and suitablefractions reacted with the phosphorus sulfide to obtain the desiredreaction products. The bottoms resulting from the fractionation of thepolymer may have Saybolt Universal viscosities at 210 F. ranging from 50seconds to about 10,000 seconds and are well suited for the purpose ofthe present invention.

Essentially paraffinic hydrocarbons such as bright stock residuums,lubricating oil distillates, petrolatums, or paraffin waxes may be used.There can alsobe employed the condensation products of any of theforegoing hydrocarbons, usually through first halogenating thehydrocarbons and then reacting with aromatic hydrocarbons in thepresence of anhydrous inorganic halides, such as aluminum chloride, zincchloride, boron fluoride and the like.

Examples of high molecular weight olefinic hydrocarbons which can beemployed as reactants are cetene (C and cerotene (C melene (C and mixedhigh molecular alkenes obtained by cracking petroleum oils.

. Other preferred olefins suitable for the preparation oftheherein-described phosphorus sulfide reaction products are olefinshaving at least carbon atoms in the molecule of which from about 13carbon atoms to about 18 carbon atoms, and preferably at least 15 carbonatoms, are in a long chain. Such olefins can be obtained by thedehydrogenation of parafiins, such as by the cracking of paraffin waxes,or by the dehydrohalogenation of alkyl halides, preferably long chainalkyl halides, particularly halogenated parafiin waxes.

The olefins obtained by dehydrohalogenation of long chain alkyl halidesare preferably those' obtained by dehydrohalogenation-of monohalogenatedwaxes, such as for example, those obtained by dehydrochlorination ofmonochlorparafiin wax. The alkyl halides are decomposed to yield olefinsaccording to the reaction in which n is a whole number, preferably 20 ormore, and X is a halogen. It is preferred to employ parafiin waxeshaving at least about 20 carbon atoms per moleeule, and melting pointsupwards from about F. to about F.

To obtain the halogenated parafiin wax, for example, chlorinatedparafiin wax, chlorine is introduced into the wax, maintained in amolten state, until the wax has a chlorine content of from about 8% toabout 15%. The chlorinated wax product is a mixture of unchlorinatedwax, monochlor wax and polychlor wax. This chlorinated product may beused as such, but it is advantageous to use the substantially monochlorwax fraction. The monochlor wax fraction can be segregated from theunchlorinated wax and the polychlor wax fractions by taking advantage ofthe differences in the melting points of the various fractions, sincethe melting point of the wax varies with the extent of chlorination,i.e., the melting point of the unchlor nated wax is greater than that ofthe monochlor wax, and the melting point of the latter is greater thanthat of the polychlor wax. Thus, the monochlor paratfin wax can beseparated from the unchlorinated and the polychlor wax fractions bymeans such as sweating, fractional distillation, solvent extraction,solvent precipitation, and fractional crystallization. The highmolecular weight olefins are obtained by removing the halogen ashydrogen halide from the halogenated paratfin wax. For example, thecorresponding olefin is obtained from the monochlor paraflin wax byremoving the chlorine from'the latter as hydrogen chloride. Themonochlor wax can be dehydrochlorinated by heating to a temperature offrom about 200 F. to about 600- F. in the presence of adehydrochlorinating agent such as an alkali metal hydroxide or analkaline earth metal hydroxide or oxide. Other alkaline inorganic ororganic materials can also be used. The chlorine can also be removedfrom the chlorowax by heating the same for a prolonged period in theabsence of any dehydrochlorinating agent. After the dehydrohalogenationhas been completed, the olefin so obtained can be further purified byremoving the dehydrohalogenating agent by means of filtration or byother suitable means.

As other starting materials there can be used the polymer or syntheticlubricating oil obtained by polymerizing unsaturated hydrocarbons,resulting'from the vapor phase cracking of paralfin waxes, in thepresence of aluminum chloride, which is fully described in United StatesPatents vention are the reaction products of a' phosphorus sulfide withan aromatic hydrocarbon such as for example benzene, naphthalene,toluene, xylene, diphenyl and the like, or with an alkylated aromatichydrocarbon such as, for example, benzene having an alkyl substituenthaving at least four carbon atoms and preferably at least eight carbonatoms such as, for example, long chain parafiin waxes, olefin polymersand the like.

The phosphorus sulfide-hydrocarbon reaction product can be readilyobtained by reacting a phosphorus sulfide, for example, P 8 with thehydrocarbon at a temperature of from about 200 F. to about 500 F. andpreferably from, about 200 F. to about 400 F., using from about 1% toabout 50% and preferably'from about 5% to about 25% of the phosphorussulfide in the reaction. It is advantageous to maintain a non-oxidizingatmosphere such as, for example, an atmosphere of nitrogen above thereaction mixture. Usually it is preferable to use an amount of thephosphorus sulfide that will completely react with the hydrocarbon sothat no further purification becomes necessary; however, an excessamount of phosphorus sulfide can be used and separated from the productby filtration or by dilution with a solvent such as hexane, filteringand subsequently removing the solvent by suitable means such as bydistillation. if desired, the reaction product can be further treatedwith an agent having an active hydrogen atom such as steam at anelevated temperature of from about 100 F. to about 600 F.

The phosphorus sulfide-hydrocarbonreaction product normally shows atitratable acidity which is neutralized by treatment with a basicreagent. The phosphorus sulfide-hydrocarbon reaction product whenneutralized with a basic reagent containing a metal constituent ischaracterized by the presence or retention of the metal constituent ofthe basic reagent. Other metal constituents such as a heavy metalconstituent can be introduced into the neutralized product by reactingthe same with a salt of the desired heavy metal.

The term neutralized phosphorus sulfide-hydrocarbon reaction product asused herein means a phosphorus sulfide-hydrocarbon reaction producthaving at least about 1% of its titratable acidity neutralized byreaction with a basic reagent and includes the neutralized phosphorussulfide-hydrocarbon reaction products containing a metal constituentresulting from said neutralization or resulting from the reaction of aheavy metal salt with the phosphorus sulfide-hydrocarbon reactionproduct treated with a basic reagent.

The neutralized phosphorus sulfide-hydrocarbon reaction product can beobtained by treating the reaction product with a suitable basic compoundsuch as a hydroxide, carbonate, oxide or sulfide of an alkaline earthmetal or an alkali metal such as, for example, potassium hydroxide,sodium hydroxide, sodium sulfide, etc. Other basic reagents can be usedsuch as, for example, ammonia or an alkyl or aryl substituted ammoniasuch as amines. The neutralization of the phosphorus sulfidehydrocarbonreaction product is carried out preferably in a non-oxidizing atmosphereby contacting the reaction product either as such or dissolved in asuitable solvent such as naphtha with a solution of the basic reagent,for example, potassium hydroxide or sodium hydroxide dissolved inalcohol. As an alternative method, the reaction product can be treatedwith solid alkaline compounds such as KOH, NaOH, Na CO K CO CaO, Na S,and the like at an elevated temperature of from about 100 F. to about600 F. As was aforesaid, when the phosphorus sulfide-hydrocarbonreaction product is neutralized with a basic reagent containing a metalconstituent, the neutralized reaction product is characterized by thepresence of the metal constituent of the basic reagent. Neutralizedreaction products containing a heavy metal constituent such as, forexample, tin, titanium, aluminum, chromium, cobalt, zinc, iron, and thelike,

can beobtained by reacting a'salt of the desired heavy metal with'thephosphorus sulfide-hydrocarbon reaction product-which has been treatedwith a basic reagent. It will be understood that When the neutralizationis accomplished with a polyvalent basic material such'as lime, a producthaving excess basicity may be obtained.

The neutralized phosphorus sulfide-hydrocarbon reaction product can beprepared by the method described in U.S. 2,688,612 issued to Watson onSeptember 7, 1954,

The reaction product of a basic metal'compound, a hydroxy compound andcarbon dioxide of the hereinbefore described class which is used incombination with the neutralized reaction product of a phosphorussulfide and-a hydrocarbon is a preferentially oil-soluble product. Oneof the classes ofhydroxy compounds, as pointed out hereinbefore, is thealkyl phenols having from 8 to 36 carbon atoms andpreferably from about12 to about 26 carbon atoms. Thus the substituted phenol may contain oneor more side chains and the total number of carbon atoms in the sidechains may be from about 2 to about 30. These alkylated phenols may beobtained by any of the conventional methods for preparing suchcompounds; for instance, they may be alkylated in the presence ofaluminum chloride or the like. Inasmuch as the method of preparing thealkylated phenols is not germane to this invention, they. may beobtained in any manner or by any method. The alkyl groups on suchalkylated phenols are provided to increase the oil solubility andviscosity characteristics of the compound. Hence they may be,substituted on more than one of the carbon atoms of the aromaticnucleus. For instance, the alkylated phenols may range from ethyl phenolto dinonyl phenol or trihexyl phenol or the like or any combination ofsubstituents provided that the required solubility and viscositycharacteristics are obtained.

Another class of hydroxy compounds referred to hereinbefore is the alkylalcohols having 5 to 30 carbon atoms, and preferably from about 8 toabout 20 carbon atoms. Neither the number of the carbon atoms in thealkyl group nor their configuration is critical provided thattherequisite oil solubility and viscosity characteristics are provided. 2

. The reaction of a basic reagent having a metal constituent with thehereinbefore described hydroxy containing hydrocarbons may be carriedout Within Wide temperature limits; for example, temperatures as low as0 F. and as high as 400 F. may be employed, although temperatures withinthe range of from about'100 F. to about 350 F. are generally preferred.Carbon dioxide is reacted with the metal containing compound at atemperature in the range of from about 0 F. to about 300 F., althoughtemperatures within the range of about F. to about 250 F. are preferred.

The following reactions are proposed to'facilitate comprehension of theinvention, but they are in no Wayto be considered limitative ordefinitive. A hydroxy'compound of the class described hereinbefore isreacted with a basic metal compound, such as, for example, barium oxide,thereby forming a normal or basic barium salt of such hydroxy containingcompound depending upon the relative amount of barium reacted with thehydroxy compound; this reaction product is then contacted with carbondioxide to form a normal or basic barium carbonate, bicarbonate or thelike. In view of the mild reaction conditions used, i.e., carbonation atessentially atmospheric pressure and at a temperature not exceedingabout 300 F., a carboxylation reaction is not contemplated; such acarboxylation reaction would result in the formation of alkylsubstituted, carboxylated phenols.

To more fully illustrate the preparation of the reaction product of abasic metal compound, a hydroxy compound and carbon dioxide, thefollowing examples are presented. Although barium is employed in theexamples,,itjis-to be understood that other metals may be employed. .For instance, any of the alkaline earth metals,

alkali metals or heavy metals such as; for example, tin,

titanium, aluminum, chromium, cobalt, zinc, iron and 'of the invention.

. EXAMPLE I One mol (130 g.) of 2-ethyl hexyl alcohol was treated with0.5 mol (78 g.) of barium oxideat 230 F. in the presence of 0.5 to 1.0cc. of water. A very rapid temperature rise to 300 F. resulted within ashort time after the barium oxide was added. The temperature wasmaintained at 300-320? F. for a period of 4 hours. The barium alcoholatewas cooled to 160 Rand treated with CO for 1 hour at a temperature ofl40-l60 F. The resulting product was diluted with 50 ml. of benzene andfiltered to remove unreacted barium salts. After removal ,of the benzeneby distillation, the. product contained 27.19% barium. t EXAMPLE IIEXAMPLE III 2.5 mols (515 g.) of octylphenol was reacted with 2.5 molsof barium oxide (420 g. of a mixture containing about BaCO in thepresence of 935g. of solvent extracted SAE-S base oil at a temperatureof about 300 F. for a period of 4 hours. The reaction mixture was cooledto about 200 F. and treated with CO. Unreacted barium salts were removedand'the oil-diluted product was found to contain 11.91% barium. Thisrepresents more than the calculated amount of barium to form the normalsalt. Thus the product was a basic barium salt, 20% alkaline.

EXAMPLE IV Forty grams of BaO were added to 117 g. of diamyl phenol at230 F. Water (1 g;) was added and the temperature slowly increased to300 F. After stirring for 2 hours at 300 F., the barium diamylphenatewas cooled to 140-175 F., diluted with 150 cc. of benzene and treatedwith a stream of CO for 6 hours. The product was filtered and thesolvent removed by distillation. The

'8 product, a'viscous brown liquid, contained 25.3% Ba. It iscontemplated that various other of the well known corrosion inhibitors,anti-oxidants, anti-foaming agents, pour point depressors, extremepressure agents, anti-wear agents, V.I. improvers, etc. may beincorporated in lubricating oils containing the additives of ourinvention.

As pointed out hereinbefore, compositions containing our additives haveexcellent detergencycharacteristics. Engine tests'were made todemonstrate this efiect using the following compositions:

Example A.-SAE 30 solvent extracted base oil containing 1.65% of abarium containing neutralized P S butene polymer (3000 SUS at 210 F. anda molecular weight of about 940') reaction product and 0.5% sulfurizeddipentene.

Example B.-Same as Example A but containing 3.30% of thebarium-containing neutralized P s -butene polymer.

Example C.Example A plus 0.85% of (oil free basis) the product ofExample III. I

Example D.Example A plus 0.67% of the product of Example I.

Example-E.Example A plus 1.17% of the product of Example I. Y

These tests were made on a single cylinder Caterpillar engine accordingto a modified L-l test procedure. operating for hours at l,000'r.p.m.with a load of 19.8 B.H.P., with an oil sump temperature of l45-l50 F.and a'water outlet temperature of -180 F. In all of the tests a fuelhaving 1% sulfur was employed. The results of these tests are shown onTable I. The engine ratings employed give the actual percentage ofcarbon deposits'in the ring grooves. The lacquer ratings, however, takeinto consideration the type of lacquer, i.e., light, amber or dark.

The data shown in Table l demonstrate the improvement in lacquer ratingwhen employing the reaction product of a basic metal compound, a hydroxycompound and carbon dioxide with the'neutralized reaction product of aphosphorus sulfide and a hydrocarbon.

Concentrates of a suitable lubricating oil base containing from about10% to about 50% 'or more of the hereindescribed additive, alone or incombination with various amounts of other additives, can be used forblending with other hydrocarbon lubricating oils or otherrlubricatingoil bases'in' the proportion desired for the particular conditions ofuse to give a finished p'roduct containing from about 0.01% to about 20%of the mixture of the neutralized reaction product of a phosphorussulfide and a hydrocarbon, and the reaction product of a basic metalcompound, a hydroxy compound and carbon dioxide.

While the present invention has been described by the use of ourcomposition in petroleum lubricating oils, other lubricating oil bases'maybe employed such as hydrocarbon oils, natural or synthetic, such asthose obtained by the polymerization of olefins, as well as syntheticlubricating oils of the alkylene oxide types, and the Table I I I[Caterpillar engine tests, L-l. 120 hours, 1% sultutr fuel. ]SAE. 30solvent extracted base oi1+0.5% suliurized erpene. I l I Engine Rating IAdditive Additive Composition Coucen- Top Groove 2nd Groove tration, 3rd

percent Groove, Carbon, Lacquer Carbon. Lacquer Lacquer Percent PercentExample {Elfifffliifiiii 11 .332 7 I f 93 25 e -----{dliiffifiifii 53336 0 1 0 Example {gggggfi 11 14 o a o Ba-P S'-Olefin 1.65 Example 1)----{g i gig g I 1 21 o s 0 Example O:i8n i)i B :C i) 1117 3 polycarboxylicacid ester type oils such as the oil-soluble esters of adipic acid,sebacic acid, azelaic acid, etc.

Unless otherwise stated, the percentages stated herein and in the claimsare weight percentages.

Although the present invention has been described with reference tospecific preferred embodiments thereof, the invention is not to beconsidered as limited thereto, but includes within its scope suchmodifications and variations as come within the spirit of the appendedclaims.

We claim:

1. A lubricant composition having improved detergency properties andsuitable for use in an internal combustion engine operating on a highsulfur fuel, said lubricating composition comprising a major proportionof a lubricating oil and in combination therewith an amount within therange of from about 0.001 to about 10% suflicient to impart detergencyof a neutralized phosphorus and sulfur-containing reaction product of aphosphorus sultide and a butene polymer obtained by reacting aphosphorus sulfide with a butene polymer and subsequently neutralizingthe reaction product with a basic reagent containing a metalconstituent, and from about 0.01% to about 2% of a compound prepared byreacting a basic metal compound and a monohydroxy compound selected fromthe group consisting of alkyl alcohols having from about 8 to about 20carbon atoms and alkyl phenols having from about 12 to about 26 carbonatoms and contacting said reaction product with carbon dioxide at atemperature of from about 0 F. to about 300 F.

2. A lubricant composition having improved detergency properties andsuitable for use in an internal combustion engine operating on a highsulfur fuel, said lubricating composition comprising a major proportionof a lubricating oil and in combination therewith an amount within therange of from about 0.001 to about 10% suflicient to impart detergencyof a neutralized phosphorus and sulfur-containing reaction product of aphosphorus sulfide and a mono-olefin polymer obtained by reacting aphosphorus sulfide with a mono-olefin polymer and subsequentlyneutralizing the reaction product with a basic reagent containing ametal constituent, and from about 0.01% to about 2% of a compoundprepared by reacting a basic metal compound and a monohydroxy compoundselected from the group consisting of alkyl alcohols having from about 8to about 20 carbon atoms and alkyl phenols having from about 12 to about26 carbon atoms and contacting the resulting product with carbon dioxideat a temperature of from about 0 F. to about 300 F.

3. The lubricant composition of claim 1 wherein the monohydroxy compoundis 2-ethylhexanol.

4. The lubricant composition of claim 1 wherein the monohydroxy compoundis nonyl alcohol.

5. The lubricant composition of claim 1 wherein the monohydroxy compoundis octyl phenol.

6. The lubricant composition of claim 1 wherein the monohydroxy compoundis diamyl phenol.

References Cited in the file of this patent UNITED STATES PATENTS2,252,664 Reiff Aug. 12, 1941 2,365,011 Rosen Dec. 12, 1944 2,422,585Rogers June 17, 1947 2,647,889 Watson Aug. 4, 1953 2,762,774 PopkinSept. 11, 1956

1. A LUBRICANT COMPOSITION HAVING IMPROVED DETERGENCY PROPERTIES ANDSUITABLE FOR USE IN AN INTERNAL CONBUSTION ENGINE OPERATING ON A HIGHSULFUR FUEL, SAID LUBRICATING COMPOSITION COMPRISING A MAJOR PROPORTIONOF A LUBRICATING OIL AND IN COMBINATION THEREWITH AN AMOUNT WITHIN THERANGE OF FROM ABOUT 0.001 TO ABOUT 10% SUFFICIENT TO IMPART DETERGENCYOF NEUTRALIZED PHOSPHORUS AND SULFUR-CONTAINING REACTION PRODUCT OF APHOSPHORUS SULFIDE AND A BUTENE POLYMER OBTAINED BY REACTING APHOSPHORUS SULFIDE WITH A BUTENE POLYMER AND SUBSEQUENTLY NEUTRALIZINGTHE REACTION PRODUCT WITH A BASIC REAGENT CONTAINING A METALCONSTITUENT, AND FROM ABOUT 0.01% TO ABOUT 2% OF A COMPOUND PREPARED BYREACTING A BASIC METAL COMPOUND AND A MONOHYDROXY COMPOUND SELECTED FROMTHE GROUP CONSISTING OF ALKYL ALCOHOLS HAVING FROM ABOUT 8 TO ABOUT 20CARBON ATOMS AND ALKYL PHENOLS HAVING SAID ABOUT 12 TO ABOUT 26 CARBONATOMS AND CONTACTING SAID REACTION PRODUCT WITH CARBON DIOXIDE AT ATEMPPERATURE OF FROM ABOUT 0*F. ABOUT 300*F.